Gasoline containing a methyl phenol and an ether

ABSTRACT

A useful fuel for an internal combustion engine comprises a hydrocarbon base stock of gasoline boiling range, a methylsubstituted phenol and an ether containing a branched alkyl group and boiling below 460*F., said phenol and said ether each being present in amount (e.g., 0.1-15 wt. %) sufficient to increase the Research octane number (RON). The invention also includes a gasoline blending system. For example, preferred compositions can be made by blending 89 RON gasoline containing 5 vol. % p-cresol with 97 RON gasoline containing 5% methyl methoxy propane. Beneficial synergism is noted in such blends for RON blending values.

States Patent Shang et al.

[ GASOLINE CONTAINING A METIIYI PHIENOL AND AN ETHER [75] Inventors:Jer-Yu Shang; Barry A. Bisson, both of Wilmington, Del.; RaymondWynkoop, Gladwyne, Pa.

[73] Assignee: Sun Research and Development Co.,

Philadelphia, Pa.

[22] Filed: June 23, I972 [21] Appl. No.: 265,850

3,030,195 4/1962 Ewan 44/56 3,224,848 12/1965 Henderson 44/56 OTHERPUBLICATIONS Unzelman et 211., Are there substitutes for leadantiknocks? May 14, 1971, p. 888, API Division of Re- [451 Sept. 17,I974 fining Proceedings.

Van Winkle, Matthew, Aviation Gasoline Manufacture, 1944, p. 199, McGrawHill Book Company.

Primary Examiner-Patrick P. Garvin Assistant Examiner-Andrew H. MetzAttorney, Agent, or FirmMr. George L. Church; Mr. J. Edward Hess; Mr.Barry A. Bisson [5 7 ABSTRACT A useful fuel for an internal combustionengine comprises a hydrocarbon base stock of gasoline boiling range, amethyl-substituted phenol and an ether containing a branched alkyl groupand boiling below 460F., said phenol and said ether each being presentin amount (e.g., 0.1-15 wt. sufficient to increase the Research octanenumber (RON). The invention also includes a gasoline blending system.For example, preferred compositions can be made by blending 89 RONgasoline containing 5 vol. p-cresol with 97 RON gasoline containing 5%methyl methoxy propane. Beneficial synergism is noted in such blends forRON blending values.

13 Claims, 2 Drawing Figures PATENILUSEP mam SHEET 1 BF 2 FIG.

O BASE STOCK U BASE STOCK 5% WT. MIXTURE A BLENDING VALUE 5 5% WT.MIXTURE VOL.% HIGH RON BASE 5% MMOP PAIENIED 3, 8 36.342

sum 2 [IF 2 FIG. 2

O BASE STOCK 87 R 0 BASES P-CRESOL a MMOP A BLENDING VALUES MOTOR OCTANENUMBER I I I 0 25 5o 75 I00 VOL. LOW RON BASE 5% P-CRESOL l I l I I00 75so 25 o VOL. HIGH RON BASE 5% MMOP MOTOR BLENDING VALUES GASOLINECONTAINING A METHYL PHENOL AND AN lETK-llER SUMMARY OF THE INVENTION Theinvention includes a novel gasoline blending systern, the use of thissystem to produce motor fuel of improved octane rating, and novelgasoline compositions containing certain phenols and ethers.

One embodiment is gasoline comprising a hydrocarbon base stock ofgasoline boiling range, a methyl substituted phenol and an ether havingat least one branched alkyl group and boiling below 460F., said phenoland said ether each being present in amount sufficient to increase theResearch octane number.

Another embodiment is a gasoline blending system comprising a supply ofa relatively high Research octane number gasoline containing an octaneimproving amount of an ether boiling below 460F., and a supply of arelatively low Research octane number gasoline containing an octaneimproving amount of a methyl substituted phenol boiling below about460F., and means for blending said two supplies to produce gasolineshaving octane numbers intermediate to those of said high and low octanenumber gasolines.

The preferred methyl substituted phenols include the cresols (e.g.,p-cresol), the xylenols (e.g., 2,3 dimethyl phenol) and thetrimethyl-substituted phenols (e. g., hydroxy pseudocumene, hydroxymesetylene, and hemimelitol) and mixtures of such phenols, with thecresols being the preferred additives to a low RON hydrocarbon basestock in our blending system where the high RON hydrocarbon basecontains an ether additlve.

The preferred ethers comprise the dialkyl ethers wherein at least onealkyl group is branched, and include diisopropyl ether, diisobutylether, methyl isopentyl ether, methyl isopropyl ether, and mixtures oftwo or more said ethers. Phenyl alkyl ethers can also be used (e.g.,isopropyl phenyl ether). One non-branched alkyl phenyl ether, methylphenyl ether (methoxy benzene) can be used in a gasoline containing amethyl phenol or as the ether in the blending system described herein.

The ethers and phenols which can be used in our invention include thosedescribed by G. H. Unzdman, E. .l. Forster and A. M. Burns, in AP!Preprint (Div. of Refining) No. 47-71, titled Are There Substitutes forLead Antiknocks, presented at the API Meeting in San Francisco, May 14,1971.

Generally, the amount of the ether can be in the range of 0.05-30% andthe amount of the phenol in the range of 0.05-35% (the limit beingdetermined by solubility); however, the preferred amounts are in therange of 0. ll%. More preferred, the phenol is in the range of 0.5- wt.and the total of said amounts is in the range of 1-15 wt.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying FIGS. 1 and 2illustrate the beneficial synergistic effect on research octane blendingand motor octane blending values which can be obtained by practice ofthe blending system of the present invention wherein the low RONgasoline contains p-cresol and the high RON gasoline contains methylmethoxy propane.

As is described in more detail hereinafter, the data for FIGS. l and 2were obtained with gasoline base stocks of slightly differentcomposition and are presented for purposes of illustration. If desired,the data in Table 2 herein can be plotted, in a manner similar to FIG.1, to provide a comparison of RON and MON blending values for the samegasoline bases.

FURTHER DESCRIPTION In a preferred blending system the low RON gasolinecontains a cresol (or mixture of cresols) and preferably containsp-cresol (typically, l-l5 wt. more preferred 2-10 wt. and the high RONgasoline contains methyl tertiary butyl ether, methyl methoxy propane(MMOP), typically 1-20 wt. more preferred 2-15 wt. (e.g., 7%).

The gasolines can also contain a lead antiknock e. g., 0.1-4 cc.TEL/gal), a lead scavenger (e.g., organo bromides, ethylene dichloride),deposit modifiers (e.g., boron and phosphorous compounds), lower acyclicalcohols (e.g., methanol, ethanol, isopropanol, butanol, etc.), a leadappreciator (e.g., t-butylacetate), oxidation inhibitors (e.g., aromaticamines and/or alkyl phenols, such as 2,6-di-t-butyl-p-cresol), metaldeactivators (e.g., NN-disalicylidene-l,2-propylene diamine), corrosioninhibitors (e.g., high molecular weight phosphoric, carboxylic or sulfonic acids or their reaction products with nitrogen bases, such as amines,and include Ethyl MPA), antistatic additives (e.g., Shell ASA-3") andanti-icing additives (e.g, methylcellosolve and glycerol). Some of thesegasoline additives are described, for example, by J. P. Heuston,Chemical Additives in Petroleum Fuels, S. African Ind. Chemist,20:65-70, 74 (1966).

In our gasoline blending system, one or both of the gasolines cancontain an acyclic alcohol containing in the range of 1-4 carbon atomspreferably the supply which contains the ether contains in the range ofll5 wt. of the alcohol. Such alcohols increase the RON of the gasolines.

In the blending system, on a lead free basis the high RON gasoline willtypically have an RON in the range of 90-105 and the low RON gasolinewill be at least 5 RON lower. However, where one: or both gasolinescontain a lead antiknock compound (such as mixed methyl and ethyl leads,e.g., dimethyl diethyl lead, etc.), the high RON gasoline can have anRON as high as 120 (the low RON gasoline being, typically, in the rangeof 75-90 RON).

In our blending system, typically, the hydrocarbon base of the high RONgasoline can contain in the range of 20-40% aromatics, 0-20% olefins,0-l0% naphthenes, with the balance being para'ffins (the minimumparaffin content being 45%, more preferred 55%). The low RON gasolinecan contain in the range of 15-40% aromatics, 025% olefins, 2-20%naphthenes, with the balance being paraffms, the minimum paraffincontent being 35% (more preferred 45%).

In our preferred gasoline compositions, containing both the ether andphenol (such as the blends from our system), the preferred hydrocarbonbase stock contains in the range of 40-75% paraffins, 0-10% naphthenes,0-20% olefins and 20-40% aromatics. More preferred, the base stock willhave an RON in the range of -100, and an MON in the range of 75-95. Forthe synergistic effect disclosed herein with p-cresol and MMOP, thepreferred base stock contains in the range of 50-60% paraffins, 1-10%naphthenes, 2-l0% olefins and 28-38% aromatics.

ILLUSTRATIVE EXAMPLES EXAMPLE 1 Typical low Research octane rating andhigh Research octane rating hydrocarbon base stocks, in the gasolineboiling range, were obtained by blending selected refinery streams,including catalytically cracked gasoline, straight run gasoline,reformate, aviation alkylate, etc.

Table 111 reports the percentages by volume of paraffins, naphthenes,olefins and aromatics in these base stocks. Table IV reports in moredetail on the composition of a stabilized sample of each blend stock.

Methyl methoxy propane (MMOP) was added, 5 wt. to a sample of the highRON base stock and pcresol, 5 wt. was added to a sample of the low RONbase stock.

A series of blends was made of various proportions of the high RON basewith the low RON base and of the high RON base plus 5% MMOP with the lowRON base plus 5% p-cresol.

Research octane ratings were obtained for each of the base stocks andblends. The significance of the blending value octane number and itsmethod of calculation are described in US. Pat. No. 3,030,195, issued4-17-62 to Evan B. Ewan. The blending value RON was then calculated forselected blends. The results of these tests and calculations arereported in Table l and are summarized by the curves in FIG. 1. Abeneficial synergistic effect was noted for the RON blending values of30 the blends containing both p-cresol and MMOP.

'There was an insufficient amount of the two hydrocarbon bases to permittesting for motor octane number (MON).

EXAMPLE 2 High and low RON hydrocarbon base stocks, in the gasolineboiling range, were obtained by blending the same types of selectedrefinery streams and in about the same proportions as in Example 1.Since the refinery streams were not identical to those used in theExample bases, the chemical compositions and octane ratings were not thesame as in Example 1, but represent the usual variation which isencountered in refining practice. 5 wt. pscresol was added to a sampleof the low RON base and,-l5 lwt. MMOP was added to the high RON base.The tiivo gasolines were blended as in Example 1 and both research (RON)and motor (MON) octane numbers were obtained. Research and motorblending values were calculated. Table 11 reports the results of thesetests and calculations. Slight synergism (in comparison with Example 1)was noted in the RON blending values for some blends and greatersynergism (but less than in Example 1) was noted for most blends in theMON blending values. FIG. 2 presents curves summarizing the results ofthe motor octane number testing of this example.

Table V attached hereto presents analyses of typical refinery streamswhich can be used to make hydrocarbon base stocks which can be used inthe present invention. Table V also shows proportions for blending thesestreams to make a high RON and a low RON base which are particularlydesirable in our blending system.

20 The low RON base analyzes (in volume paraffins, 7% naphthenes, 15%olefins and 38% aromatics. The high RON base contains 63% paraffins, 0%naphthenes, 3% olefins and 34% aromatics.

In gasoline for automobiles-using conventional piston engines, it hasbeen found that knocking under actual road conditions (or road octane)can be better correllated with a function such as R+M/2 or R+2M,/2,which combines RON (i.e., R) and MON (i.e., M), than with either RON orMON. Therefore, it is apparent that both of the previous examplesindicate that the present blending system and gasolines can provideimproved performance in an automobile under actual road conditions.

Among the cresols, the ortho and meta isomers are less preferred ingasoline than p-cresol. That is, paracresol has higher research andmotor octane blending values (and lower sensitivity) than the otherisomers. Each of these isomers can absorb (or dissolve) in the order of2 wt. water and, with about 15 wt. cresols in gasoline the watersolubility is about 0.5 wt If this amount of water is added to thegasoline, it reduces flame temperature and, thus, the NOx (nitrogenoxides) emission and increases the power output of the engine.

TABLE I p-CRESOL AND METHYL t-BUTYL ETHER 1N GASOLINE BLENDS BaseComposition (Volume C D E F RUN A B G H Low RON Base Stock 5% Wt.p-Cresol 85.7 71.4 57.1 42.9 28.6 14.3 High RON Base Stock 5% Wt. MMOP100 14.3 28.6 42.9 57.1 71.4 85.7 Research, F-1 Clear Duplicates 89.097.8 90.4 91.6 93.0 94.6 95.6 97.0 89.1 97.8 90.6 91.8 93.0 94.6 95.696.8 Average 89.05 97.8 90.5 91.7 93.0 94.6 95.6 96.9

A B C D E F G H Low RON Base Stock 100 85.7 71.4 57.1 42.9 28.6 14.3High RON Base Stock 100 14.3 28.6 42.9 57.1 71.4 85.7 Research, F-lClear Duplicates 83.6 96.3 85.2 87.0 88.9 90.3 92.0 93.6 83.8 96L 85.487.0 88.8 90.4 92.0 93.6 Average 83.7 96.25 85.3 87.0 88.85 90.35 92.093.6 Increased RON 5.35 1.55 5.20 4.70 4.15 4.25 3.60 3.30 BlendingValue RON 191 127 189 181 172 175 164 TABLE II p-Cresol and methylmethoxy propane (MMOP) in gasoline blends (All concentrations in volumepercent, unless otherwise noted) Blend No 1 2 3 4 5 6 7 8 9 10 11 12 1814 15 16 Low Octane Base 100 85.7 71.4 57.1 42.9 28.6 14 3 LOB plus 5%wt.

p-cresol 100 85- 7 7 4 57. 1 42. 9 28. 6 14,3 High Octane Base H0 10014.3 28.6 42. 9 57.1 71.4 5,7 HOB plus 5% wt.

MMOP 100 14.3 28.6 42.9 57.1 71.4 35 7 Research (RON):

Cl r 84. 9 89. 2 95. 2 96. 6 86. 0 90. 2 87. 5 90. 9 89. 1 91. 8 90. 803. 4 9'1. 9 94. 5 93, 7 95, 4 Duplicate 85. 0 89. 2 95. 2 96. 6 86. 090. 3 87. 5 91. 2 89. 2 92. 0 91. 0 93. 3 92. 0 94. 4 93. 6 95. 4Average 84. 95 89. 2 95. 2 96. 6 86. 0 90. 87. 5 91. 0.5 89. 15 91. 990. 9 93. 91. 95 94. 65 4 Blndg.value RON 169.95 123.2 171.0 1 8.5144.15 139.9 141.85 128.65 Motor (MON) clear. 78. 0 82. 0 85. 6 86. 078. 7 82. 7 79. 5 83. 3 81. 1 83. 9 82. 4 84. 3 83. 4 84. 9 84. 0 85. 4Duplicate 78. 0 82.0 85.3 86. 0 78. 9 82. 4 78. 8 83. 0 81. 2 83. 8 82.4 84. 3 83. 4 84. 9 84. 3 85. 5

Average 78.0 82.0 85.45 86.0 78.8 82. 78. 83. 15 81. 15 83. i5 .4 83. 484. 9 84. 15 85. 45 Blndg. value MON 8.0 110. 15 Sensitivity R-M. 6.957. 20 9. 9. 95 B.V. sensitivity 05 18. 50

TABLE 111 GASOLINE COMPOSITION (VOLUME PERCENT) 25 Blends (Base Stocks)Low RON High RON Paraffims 55 58 Naphthenes 9 6 Monocyclic paraffins 8.81.9 Olefins l0 4 di-cyclic paraffms 0.6 0.1 lQfiL 25 32 tri-cyclicparaffins 0.1 0 TOTAL 100 100 3 Olefins 9.6 3.7 Research Octane (RON)Aliphatic monoolefins 7.6 3.2 Mmor Octane (MON) 78 85 Cyclic monoolefins2.0 0.5 Aromatics 30.2 34.6

(Alkyl Benzenes) (29.2) (34.4) v Benzene 1.1 0.5 Toluene 5.5 15.8 350,35 I00 TABLE IV C s 8.0 5.6 CXOS 3.6 2.1 n 1.0 0.4 STAB1LlZED*GASOLINE COMPOSITION (VOLUME PERCENT) (Alkyl Naphthalene) (1.0) (0.2)

Base Stock Low RON High RON Naphthakne 5 02 0 Methyl naphthalene 0 5 0,0Paraffins 50.9 59.7 4 TOTAL 100.2 100.0

Parafflns 50.9 59.7 N112 1111161185 Stabilized by distillation to removecomponents boiling below 100F.

TABLE V Base Stock Vol.% Component Refinery Analysis (Vol. of Component)Low High Component Paraffins Naphthenes Olefins Aromatics RON RON Alkylbenzenes* 100 11.0 Reformate 35.2 0.6 0.1 64.1 10.6 25.8 CatalyticGasoline 1 1.9 8.0 20.3 59.8 63.4 Straight Run Gaso. 55.8 33.2 1.2 9.82.5 lsopentane 100 12.1 7.4 lsomerizate" 89.8 10.2 0.8 Alkylate 98.0 2.01.8 40.6 Poly Gasoline 100 0.3 2.1 Udex Raffirnate 86.8 6.4 3.6 3.2 1.0Butanes** 7.5 13.1

Typically bottoms from toluene manufacture. containing mostly xylenes(typically 50-80%) and toluene (typically 5-30%). remainder (e.g.. 5l5%)Product of hydroisomerizati of 9-15 psi). Propane can also being otheralkyl benzenes (up 10 C). on of refinery streams which contain normalparaffins (e.g., Udex raffinate).

nt can be varied to obtain the desired Reid Vapor Pressure (typically inthe range be present in winter gasoline.

The invention claimed is:

l. Gasoline comprising a hydrocarbon base stock of gasoline boilingrange, from 0.05 to 35% of a methyl substituted phenol and from 0.05 to30 of a hydrocarbyl ether having at least one branched alkyl group andboiling below 460F., said phenol and said ther each being present inamount sufficient to increase the Research octane number.

2. Gasoline according to claim 1 and wherein the amounts of said phenoland said ether are in the range of 01-15 wt.

3. Gasoline according to claim 2 and wherein the amount of said phenolis in the range of 0.1- wt. and the total of said amounts is in therange of 1-15 wt.

4. Gasoline according to claim 1 and wherein said ether is methylmethoxypropane.

5. Gasoline according to claim 1 and wherein said phenol is selectedfrom the group consisting of ortho, meta and paracresol and mixtures oftwo or more said cresols.

. 6. Gasoline according to claim 5 and wherein said ether is methylmethoxypropane.

7. Gasoline according to claim 6 and wherein said phenol consistsessentially of paracresol.

,8- .qa ql ns .3299551'195.tqslaimaniwherei aid amount of said phenol isin the range of 05-15%, said amount of said ether is in the range of0.5-1 5% and the total of said amounts is in the range of l-l6%.

9. Gasoline according to claim 8 and wherein the total of said amountsis in the range of 2-l0%.

l0. Gasoline according to claim 1 wherein said ether is selected fromthe group consisting of diisopropyl ether, diisobutyl ether, methylisopentyl ether, methyl isopropyl ether, and mixtures of two or moresaid ethers.

11. The composition of claim 1 wherein said base stock contains in therange of 40-75% paraffins, O-l 0% naphthenes, 0-20% olefins, and 20-40%aromatics.

12. The composition of claim 1 wherein said base stock has an RON in therange of 80-100 and an MON in the range of -95.

13. The composition of claim 12 wherein said base stock contains in therange of 50-60% paraffins, l-l0% naphthenes, 2-l0% olefins and 28-38%aromatics.

2. Gasoline according to claim 1 and wherein the amounts of said phenoland said ether are in the range of 0.1-15 wt. %.
 3. Gasoline accordingto claim 2 and wherein the amount of said phenol is in the range of0.1-10 wt. % and the total of said amounts is in the range of 1-15 wt.%.
 4. Gasoline according to claim 1 and wherein said ether is methylmethoxypropane.
 5. Gasoline according to claim 1 and wherein said phenolis selected from the group consisting of ortho, meta and paracresol andmixtures of two or more said cresols.
 6. Gasoline according to claim 5and wherein said ether is methyl methoxypropane.
 7. Gasoline accordingto claim 6 and wherein said phenol consists essentially of paracresol.8. Gasoline according to claim 6 and wherein said amount of said phenolis in the range of 0.5-15%, said amount of said ether is in the range of0.5-15% and the total of said amounts is in the range of 1-16%. 9.Gasoline according to claim 8 and wherein the total of said amounts isin the range of 2-10%.
 10. Gasoline according to claim 1 wherein saidether is selected from the group consisting of diisopropyl ether,diisobutyl ether, methyl isopentyl ether, methyl isopropyl ether, andmixtures of two or more said ethers.
 11. The composition of claim 1wherein said base stock contains in the range of 40-75% paraffins, 0-10%naphthenes, 0-20% olefins, and 20-40% aromatics.
 12. The composition ofclaim 1 wherein said base stock has an RON in the range of 80-100 and anMON in the range of 75-95.
 13. The composition of claim 12 wherein saidbase stock contains in the range of 50-60% paraffins, 1-10% naphthenes,2-10% olefins and 28-38% aromatics.